Thermocatalytic Hydrogen Production from Water at Boiling Condition.

Thermochemical water-splitting cycles are technically feasible for hydrogen production from water. However, the ultrahigh operation temperature and low efficiency seriously restrict their practical application. Herein, one-step and one-pot thermocatalytic water-splitting process is reported at water boiling condition catalyzed by single atomic Pt on defective In2O3. Water splitting into hydrogen is verified by D2O isotopic experiment, with an optimized hydrogen production rate of 36.4 mmol·h-1·g-1 as calculated on Pt active sites. It is revealed that three-centered Pt1In2 surrounding oxygen vacancy as catalytic ensembles promote the dissociation of the adsorbed water into H, which transfers to singlet atomic Pt sites for H2 production. Remaining OH groups on adjacent In sites from Pt1In2 ensembles undergoes O─O bonding, hyperoxide formation and diminishing via triethylamine oxidation, water re-adsorption for completing the catalytic cycle. Current work represents an isothermal and continuous thermocatalytic water splitting under mild condition, which can re-awaken the research interest to produce H2 from water using low-grade heat and competes with photocatalytic, electrolytic, and photoelectric reactions.

Impedance Spectroscopy Analysis of PbSe Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Approach.

This research endeavor aimed to synthesize the lead (II) diphenyldiselenophosphinate complex and its use to obtain lead selenide nanostructured depositions and further the impedance spectroscopic analysis of these obtained PbSe nanostructures, to determine their roles in the electronics industry. The aerosol-assisted chemical vapor deposition technique was used to provide lead selenide deposition by decomposition of the complex at different temperatures using the glass substrates. The obtained films were revealed to be a pure cubic phase PbSe, as confirmed by X-ray diffraction analysis. SEM and TEM micrographs demonstrated three-dimensionally grown interlocked or aggregated nanocubes of the obtained PbSe. Characteristic dielectric measurements and the impedance spectroscopy analysis at room temperature were executed to evaluate PbSe properties over the frequency range of 100 Hz-5 MHz. The dielectric constant and dielectric loss gave similar trends, along with altering frequency, which was well explained by the Koops theory and Maxwell-Wagner theory. The effective short-range translational carrier hopping gave rise to an overdue remarkable increase in ac conductivity (σac) on the frequency increase. Fitting of a complex impedance plot was carried out with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb), which proved that grains, as well as grain boundaries, are responsible for the relaxation processes. The asymmetric depressed semicircle with the center lower to the impedance real axis provided a clear explanation of non-Debye dielectric behavior.

Frequency stable dielectric constant with reduced dielectric loss of one-dimensional ZnO-ZnS heterostructures.

The synthesis of one-dimensional heterostructures having high dielectric constant and low dielectric loss has remained a great challenge. Until now, the dielectric performance of ZnO-ZnS heterostructures was scarcely investigated. In this work, large-scale ZnO-ZnS heterostructures were synthesized by employing the chemical vapor deposition method. High resolution transmission electron microscopy (HRTEM) confirms the formation of heterostructures. X-ray photoelectron spectroscopy (XPS) shows that S atoms fill up the oxygen vacancy (VO) in ZnO, leading to the suppression of charge carrier's movement from ZnO to ZnS; instead there is charge transfer from ZnS to ZnO. Conductivity mismatch between adjacent ZnO and ZnS materials leads to the accumulation of free charges at the interface of the heterostructure and can be considered as a capacitor-like structure. The electrical behaviors of the potential phases of ZnO, ZnS and the ZnO-ZnS heterostructure are well interpreted by a best fitted equivalent circuit model. Each heterostructure acts as a polarization node with a specific flip-flop frequency and all such nodes form continuous transmission of polarization, which jointly increase the dielectric energy-storage performance. The orientational polarization of the polarons and Zn2+-VO dipoles present at the heterostructure interface contributes to the frequency stable dielectric constant at ≥103 Hz. Our findings provide a systematic approach to tailor the electronic transport and dielectric properties at the interface of the heterostructure. We suggest that this approach can be extended for improving the energy harvesting, transformation and storage capabilities of the nanostructures for the development of high-performance energy-storage devices.

Impedance Spectroscopic Study of Nickel Sulfide Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Technique.

This research aims to synthesize the Bis(di-isobutyldithiophosphinato) nickel (II) complex [Ni(iBu2PS2)] to be employed as a substrate for the deposition of nickel sulfide nanostructures, and to investigate its dielectric and impedance characteristics for applications in the electronic industry. Various analytical tools including elemental analysis, mass spectrometry, IR, and TGA were also used to further confirm the successful synthesis of the precursor. NiS nanostructures were grown on the glass substrates by employing an aerosol assisted chemical vapor deposition (AACVD) technique via successful decomposition of the synthesized complex under variable temperature conditions. XRD, SEM, TEM, and EDX methods were well applied to examine resultant nanostructures. Dielectric studies of NiS were carried out at room temperature within the 100 Hz to 5 MHz frequency range. Maxwell-Wagner model gave a complete explanation of the variation of dielectric properties along with frequency. The reason behind high dielectric constant values at low frequency was further endorsed by Koops phenomenological model. The efficient translational hopping and futile reorientation vibration caused the overdue exceptional drift of ac conductivity (σac) along with the rise in frequency. Two relaxation processes caused by grains and grain boundaries were identified from the fitting of a complex impedance plot with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb). Asymmetry and depression in the semicircle having center present lower than the impedance real axis gave solid justification of dielectric behavior that is non-Debye in nature.

Nanostructured Lead Sulphide Depositions by AACVD Technique Using Bis(Isobutyldithiophosphinato)Lead(II) Complex as Single Source Precursor and Its Impedance Study.

This communication reports the synthesis of bis(diisobutyldithiophosphinato)lead(II) complex and its subsequent application as a single source precursor for the nanostructured deposition of lead sulphide semiconductors and its impedance to explore its scope in the field of electronics. Synthesized complex was characterized by microelemental analysis, nuclear magnetic resonance spectroscopy, infrared spectroscopy and thermogravimetric analysis. This complex was decomposed using the aerosol-assisted chemical vapour deposition technique at different temperatures to grow PbS nanostructures on glass substrates. These nanostructures were analyzed by XRD, SEM, TEM and EDX methods. Impedance spectroscopic measurements were performed for PbS in the frequency range of 40 to 6 MHz at room temperature. In a complex impedance plane plot, two relaxation processes were exhibited due to grains and grain boundaries contribution. A high value of dielectric constant was observed at low frequencies, which was explained on the basis of Koops phenomenological model and Maxwell-Wagner type polarization. Frequency-dependent AC conductivity results were compliant with Jonscher power law, while capacitance-voltage loop had a butterfly shape. These impedance spectroscopic results have corroborated the ferroelectric nature of the resultant PbS nanodeposition.